Method for producing highly pure, granular silicon in a fluidised bed

ABSTRACT

The present invention relates to a method for producing highly pure, granular silicon with a narrow particle-size distribution by decomposing silanes or halosilanes in a fluidised bed and epitaxially growing silicon on silicon seed particles, which method is characterised in that the gas containing silicon is supplied to the reaction chamber in an upward flow and the contents of the fluidised bed are separated in a continuous or discontinuous manner, whereby a particle stream from the fluidised bed is supplied to a separator mounted outside the fluidised bed, particles of the desired size are separated and undersized particles are returned to the fluidised bed. The invention also relates to a device and the use thereof for carrying out said method.

[0001] The invention relates to a method for producing highly pure, granular silicon with a narrow particle-size distribution by decomposing silicic gases in a moving-bed or fluidised-bed reactor. Furthermore the invention relates to a device and the use thereof for carrying out said method.

[0002] Silicic gases as referred to herein are gases containing silicon compounds or mixtures of silicon compounds which under the conditions according to the invention can be decomposed in the gaseous phase depositing silicon.

[0003] The growing demand for high-tech electronics and the efforts for reducing the consumption of fossil fuels by opening up alternative energy sources like solar energy has not only led to an increased demand for semiconductor materials but particularly so to a dramatic increase of the purity requirements on such substances.

[0004] Due to the good availability of the starting compounds as well as its excellent semiconductor qualities, the production of highly pure silicon for the photovoltaic area and electronics is in the focus of interest here.

[0005] A common method is the thermal decomposition of silanes or halosilanes, preferably carried out in a moving-bed or fluidised-bed reactor.

[0006] Methods wherein pure, elemental silicon is epitaxially growing on silicon seed particles by thermally decomposing silanes or halosilanes in a fluidised bed are known for example from U.S. Pat. No. 3,012,861 and U.S. Pat. No. 3,012,862.

[0007] In a fluidised-bed reactor, an initially stationary bed of solid particles, in this case silicon seed particles, is fluidised by an upward flow of gas, i.e. said bed is turned into a liquid-like state once its volume flow exceeds a certain limit depending, among other things, on the density and the diameter of the particles. This limit is called loosening velocity. The advantages of such fluidisation are, for example, the intensive mixing of particles and the large contact surface between the solid and gaseous phases.

[0008] Such silicon-containing educts used for thermal decomposition are silicon-hydrogen compounds, i.e. silanes, or halosilanes, which may be diluted by argon, helium, nitrogen or hydrogen.

[0009] The thermal decomposition of silanes is advantageous because unlike halosilanes, silanes do not require additional reducing agents and no corrosive gases like halogen hydrogens arise as by-products. In addition, the decomposition of silane occurs already in the range from 500° C., whereas most halosilanes require at least 800° C., i.e. much more energy is required.

[0010] Many applications in the photovoltaic area or in semi-conductor technology require highly pure, granular silicon with a narrow particle-size distribution.

[0011] In this context, “highly pure” means a silicon content of at least 99.99999%. The required average particle sizes are generally between 50 and 5000 μm. A narrow particle-size distribution of the silicon particles has the advantage that the further processing of such silicon, which is mainly done by remelting, requires less energy. U.S. Pat. No. 3,012,862 describes a method for producing pure silicon by decomposing halosilanes in the presence of the reducing agent in a fluidised bed. During the process of epitaxial growth, particles are formed which due to their size are not fluidised any more, but deposit on the bottom of the bed in the reactor. This process is called segregation. Through a side outlet these large particles are conducted to an external separation and, if necessary, occurring fine material is returned into the reaction zone. Such a method holds a considerable risk as a segregation on the bottom of the reactor can lead first to an agglomeration of the segregated bed contents, then during the further reaction to an agglomeration of the complete bed and finally to a termination of the process.

[0012] In U.S. Pat. No. 4,818,495, a construction is described wherein the gas required for fluidisation (fluidising gas) is blown into the reactor through a conical bottom, centrically arranged in which is a separation zone into which an upward gas stream (separation gas) is blown. JP-A 06100312 depicts another such central outward transfer. When using a central separation outlet with an upward gas feeding direction, the separation gas is introduced into the reactor at a much higher velocity than the fluidising gas. Because of the high velocity, the central flow of the separation gas is dominating and immediately attracts the gas bubbles forming of the fluidising gas in the reactor towards this central flow. There may occur a decomposition of silane or halosilanes inside the gas bubbles, however, the silicon forming there occurs in the form of very fine particles which do not bond to the surface of the seed particles. This process is called homogenous pyrolysis wherein generally particles of sizes below 50 μm are formed. As the settling speed of such fine particles is very low they are carried out by the fluidising or separation gas thus causing a loss which dramatically reduces the yield of silicon deposited on seed particles (by so-called heterogeneous pyrolysis). When working without separation gas, produce with a very broad particle-size distribution leaves the reactor through the central outlet. This means that in part particles are produced whose size exceeds the desired size by far. Furthermore some seed particles remain without any deposit.

[0013] Therefore there was a need to find a method wherein a high yield of highly pure, granular silicon with a narrow particle-size distribution suitable for use in the photovoltaic area and in semi-conductor technology can be obtained by decomposing silicic gases in a moving-bed or fluidised-bed reactor.

[0014] The invention relates therefore to a method for producing highly pure, granular silicon with a narrow particle-size distribution by decomposing silanes or halosilanes in a fluidised bed and epitaxially growing silicon on silicon seed particles, which method is characterised in that the gas containing silicon is supplied to the reaction chamber in an upward flow and the contents of the thus fluidised bed are separated in a continuous or discontinuous manner, whereby a particle stream from the fluidised bed is supplied to a separator mounted outside the fluidised bed, particles of the desired size are separated and undersized particles are returned to the fluidised bed. The invention also relates to a device and the use thereof for carrying out said method.

[0015] The special advantage of this method consists in that the fluidised contents of the bed has a narrow particle-size distribution, which reduces the risk of segregation and defluidisation. Another advantage is that the contents of the fluidised bed is finer because the particles of the desired size are carried out which encourages the formation of smaller gas bubbles. Smaller gas bubbles lead to a reduction of the unwanted dust formation thus enabling a high yield of silicon epitaxilly grown on seed particles.

[0016] The method according to the invention will now be described in more detail with reference to the exemplary embodiment depicted in FIGS. 1 and 2. This serves merely to enable a better understanding of the invention without limiting the underlying principles of the invention to any extent.

[0017]FIG. 1 shows the reactor with the gas supply (1), the braking plate (2), the apertured bottom (3), the reaction chamber (4) with the heating (5). Outside the reaction chamber, there is the seal gas supply (6) towards outlet (7) surrounded by the ring chamber (8). The separation gas supply (9) leads towards the separation tube (10) with the subsequent fine material feedback (11) discharging into the fine material cyclone (12). Below the cyclone is the fine material flap valve (13). The dust outlet (14) is located at the upper end of the reactor chamber. The bottom end of the separation tube (10) is connected to the finished product discharge valve (15) of the collecting container (16). On top of the reaction chamber (4), the seed particle pipe (17) is arranged.

[0018] According to FIG. 2, the downward outlet (7) is located above the apertured bottom (3). The seal gas supply (6) leads to the ring chamber (8) with the propulsion jet bore holes (18), which chamber surrounds the outlet (7).

[0019] According to FIG. 1, silicic gas is led to the reactor by means of the gas supply (1).

[0020] Besides silane SiH₄ and its higher homologues, as for example disilane Si₂H₆, trisilane Si₃H₈, tetrasilane Si₄H₁₀ and hexasilane Si₆H₁₄, halosilanes of the general formula SiH_(m)Hal_((4−m)) can be used, wherein m can be an integer from zero to three and Hal can be chlorine, bromine or iodine. A mixture of such silicon compounds is also suitable for the method according to the invention. Silicon compounds which are not gaseous at room temperature can be thermally transferred into the gaseous phase for example.

[0021] Silane SiH₄, disilane Si₂H₆, trisilane Si₃H₈, tetrasilane Si₄H₁₀ and hexasilane Si₆H₁₄ are preferred, silane SiH₄ is particularly preferred.

[0022] The total volume percentage of silanes or halosilanes in the introduced gas can be for example between 1% and 100%, 5 to 20 volume percent are preferred.

[0023] Furthermore the silicic gas may contain for example noble gases, e.g. argon or helium, nitrogen, other gases rendered inert under the reaction conditions or hydrogen or any mixture of such gases. Nitrogen and hydrogen are preferred, hydrogen is particularly preferred.

[0024] When using halosilanes, it must be ensured that per mol equivalent halogen at least one mol equivalent hydrogen is provided in the silicic gas. Such hydrogen equivalents can originate for example from silanes, monohalosilanes, dihalosilanes or trihalosilanes or elementary hydrogen.

[0025] The entering impulse of the silicic gas flow is refracted by the subsequent braking plate (2).

[0026] This is a common measure to ensure a steady penetration of the silicic gas flow serving as fluidising gas through the apertured bottom (3). The method according to the invention can also be carried out without such a braking plate. Other devices enabling the refraction of the impulse of the entering gas flow, e.g. deflection pipes or nozzles or another apertured bottom, are also possible.

[0027] The stream-in velocity of the introduced silicic gas should be between once to tenfold the loosening velocity required for fluidising the bed, one and a half times to seven times the speed is preferred.

[0028] The temperature of the introduced silicic gas is preferably below the temperature at which the silicic gas gets not yet decomposed. In the case of silane this is a temperature of about 300° C. The minimum introduction temperature is to be chosen such that it is at least equivalent to the boiling point of the compound based on the used partial pressure of the silicic gas, however below the respective range of decomposition.

[0029] The pressure loss of the apertured bottom (3) completing the reaction zone at its bottom end can be adjusted in a way ensuring a steady feed stream into the reaction zone of the reactor (4).

[0030] The pressure at which the method according to the invention can be carried out is uncritical. It is preferred, however, to work at pressures ranging from 50 to 50000 mbar. 100 to 10000 mbar are preferred, 200 to 6000 mbar are particularly preferred. All indicated pressure values are absolute values referring to the pressure prevailing behind the fluidized bed as seen in flow direction of the introduced gas.

[0031] The temperature of the apertured bottom should be selected such that it is below the decomposition range of the used silicon compounds during the process of epitaxial growth. Such range for silane is above approx. 300° C.

[0032] Preferably the temperature of the apertured bottom is between 20 and 300° C., particularly preferred between 200 and 250° C.

[0033] Higher temperatures can lead to silicon depositing in the apertured bottom, thus obstructing the apertures and finally to a termination of the process. The apertured bottom can be provided with several apertures ensuring a homogeneous fluidisation of the above bed by the flow of silicic gas entering the reaction zone of the reactor.

[0034] The reactor (4) is surrounded by a heating, e.g. a resistance heating (5). The heating heats up the bed such that the temperature inside the reactor is above the decomposition range of the silicic gas, however below the melting point of silicon (1414° C.). The temperature of the reactor wall is for example 2 to 200° C. higher than the temperature in the interior of the reactor, preferably between 5 and 80° C. higher.

[0035] When using silane, the advantageous temperature range in the interior of the reactor is between 500 and 1400° C., preferably between 600 to 1000° C. and particularly preferred between 620 to 800° C.

[0036] A part of the fluidised bed contents is introduced through the side outlet (7) into the separator (10), which is provided with separation gas by means of the separation gas supply (9).

[0037] Also several outlets can be provided for example. The outlet or the outlets can also be integrated for example in the apertured bottom (3).

[0038] The separator can be for example a vertical upflow separator or a zigzag separator. However, in all embodiments the separator should be located outside the fluidised bed.

[0039] The separation gas can be a gas rendered inert under the said reaction conditions, for example a noble gas, e.g. argon or helium, nitrogen, hydrogen or any mixture thereof. Nitrogen and hydrogen are preferred, hydrogen is particularly preferred.

[0040] The fines carried by the separation gas are introduced through the ascending pipe (11) into a cyclone (12), where it is deposited.

[0041] Other devices for the separation of fine material, such as filters, are also suitable for the method according to the invention.

[0042] The feedback into the reactor is carried out by means of a fine material feedback pipeline provided with a flap valve (13) which opens automatically if a sufficiently high column of fines has accumulated in the fine material feedback pipeline.

[0043] It is also possible to collect the fine material in a collecting container or to return it from the cyclone into the bed. Feedback of the fine material into the reaction zone is preferred.

[0044] Fine material is carried out of the reactor through the dust outlet (14).

[0045] Fresh seed particles can be introduced into the reaction zone through the seed particle pipe (17).

[0046] The seed particle pipe can also be arranged laterally.

[0047] Silicon particles in the separator (10) which are not led to the cyclone (12) fall down, pass through the open stop valve (15) and are collected in a collecting container (16).

[0048] The desired particle size can be adjusted according to the usual procedures by controlling the flow of separation gas.

[0049] According to FIG. 2, silicon particles can leave the fluidised bed of the reactor (4) through the lateral downward outlet (7). The penetrating amount can be controlled by means of a control gas flow introduced into the outlet (7) through the supply (6) and the ring chamber (8) as well as the bore holes (18) that are inclined at an angle relative to the outlet direction. This allows also to stop the flow completely.

[0050] This enables separation to be carried out in a continuous or discontinuous manner, a continuous separation is preferred.

[0051] For separation, an outward transfer rate is preferred corresponding to 0.1 to 15 times, preferably 0.5 to 5 times and particularly preferred 1 to 3 times the bed contents.

[0052] Control gases can be for example gases rendered inert under the reaction conditions, for example noble gases, e.g. argon or helium, nitrogen, hydrogen or any mixture thereof. Nitrogen and hydrogen are preferred, hydrogen is particularly preferred.

[0053] The amount of penetrating particles can also be controlled for example by a mechanical control valve. The outlet (7) can also be integrated in the apertured bottom (3) for example.

[0054] In the course of the process based on the method according to the invention, particles with an average desired size between 50 and 5000 μm are obtained in the collecting container (16). The particle-size distribution of the product can be such that at least 90 weight percent of the separated particles have a grain size differing from the desired size by maximum 20%. A particle-size distribution where at least 90 weight percent of the separated particles have a grain size differing from the desired size by maximum 10% is preferred.

[0055] Preferably the method according to the invention is integrated into a complex method for producing silane and highly pure silicon.

[0056] It is particularly preferred that the method according to the invention be integrated into a method for producing silane and/or highly pure silicon comprising the following steps:

[0057] 1. Trichlorosilane synthesis and subsequent isolation of the produced trichlorosilane by distillation and recycling of the unreacted silicon tetrachloride, and, if desired, the unreacted hydrogen;

[0058] 2. Disproportionation of trichlorosilane to silane and silicon tetrachloride through the intermediate stages of dichlorosilane and monochlorosilane on basic catalysts, preferably catalysts containing amino groups, carried out in two apparatuses or in one, and recirculation of the produced silicon coming out as a high-boiling component into the first reaction area.

[0059] 3. Further use of the silane of the purity achieved in the preceding step, or purification of the silane until the purity required for the intended purpose is achieved, preferably by distillation, particularly preferred by distillation under pressure.

[0060] 4. Thermal decomposition of silane to obtain highly pure silicon and method according to the invention. Starting parameters: Reactor diameter 52 mm Mass of bed 800 g Diameter of seed particles 200 μm Reaction temperature 650° C. Pressure 1 bar Silane 10 Vol % Hydrogen 90 Vol % Gas velocity 1.1 m/s

COMPARATIVE EXAMPLE 1

[0061] (Reactor without a Separator)

[0062] A laboratory reactor is run in continuous operation. Permanently seed particles (200 μm) are introduced into the reactor and product particles are discharged. At a feeding rate of approx. 5 g/h, 113 g/h product particles with an average diameter of 740 μm is produced (silane conversion: 39.7%, dust selectivity: 14.3% u/u_(mf):2.6). The particle sizes range from 200 to 1600 μm (90% passing).

EXAMPLE 2

[0063] (Reactor with Separator)

[0064] The reactor is run in continuous operation as specified in Example 1. At a seed particle feeding rate of approx. 0.8 g/h, approx. 105 g/h silicon is produced. With a separation grain of 1000 μm, an average diameter of bed particles of 770 μm and an average diameter of product particles of 1022 μm is obtained (at a reactor discharge rate of approx. 1300 g/h) (silane conversion: 41% dust selectivity: 14.4% u/u_(mf):2.8), 

Patent claims:
 1. A method for producing highly pure, granular silicon with a narrow particle-size distribution by decomposing silanes or halosilanes in a fluidised bed and epitaxially growing silicon on silicon seed particles, characterised in that the gas containing silicon is supplied to the reaction chamber in an upward flow and the contents of the fluidised bed are separated in a continuous manner, whereby a particle stream from the fluidised bed is supplied to a separator mounted outside the fluidised bed and particles of the desired size are separated.
 2. A method according to claim 1, characterised in that the separation is carried out in a discontinuous manner.
 3. A method according to claims 1 to 2, characterised in that after separation undersized particles are returned to the fluidised bed.
 4. A method according to claims 1 to 3, characterised in that the average desired size of the particles obtained by the separation process is between 50 and 5000 mm.
 5. A method according to claims 1 to 4, characterised in that at least 90% of the particles obtained by the separation process have a grain size differing from the desired average particle size by maximum 20%.
 6. A method according to claims 1 to 5, characterised in that the silicic gas flow introduced into the reactor is introduced through a reactor bottom with more than one aperture.
 7. A method according to claims 1 to 6, characterised in that the pressure prevailing in the part of the reactor located behind the fluidized bed as seen in flow direction of the silicic gas, is between 50 and 50000 mbar.
 8. A method according to claims 1 to 7, characterised in that the flow through an outlet or several outlets from the reaction zone can be controlled or blocked by a gas flow entering the outlet opposite to the outlet flow direction through one or several apertures.
 9. A method according to claims 1 to 7, characterised in that the outlet or several outlets are controlled mechanically by means of a valve.
 10. A method according to claims 1 to 9, characterised in that the separation is carried out in a vertical upflow separator.
 11. A method according to claims 1 to 9, characterised in that the separation is carried out in a zigzag separator.
 12. A method according to claims 1 to 11, characterised in that the fine material occurring during the separation process is separated from the separation gas in a dust separator.
 13. A method according to claim 12, characterised in that the fine material occurring during the separation process is separated from the separation gas in a cyclone.
 14. A method according to claims 12 to 13, characterised in that the fine material separated from the separation gas is returned to the reaction zone.
 15. A method according to claims 1 to 14, characterised in that the silicic gas contains silane SiH₄.
 16. A method according to claims 1 to 15, characterised in that the silicic gas contains hydrogen.
 17. The use of the silicon produced according to at least one of claims 1 to 16 in the photovoltaic area.
 18. The use of the silicon produced according to at least one of claims 1 to 16 in the manufacture of electronic components.
 19. A fluidised-bed reactor, characterised by the gas supply (1) with the braking plate (2), the apertured bottom (3) which forms the bottom of the reaction zone (4) and is surrounded by the heating (5), as well as by a seal gas supply (6) discharging into the ring chamber (8) which surrounds the outlet (7) with the propulsion jet bore holes (21), which outlet leads to the separation tube (10) with the separation gas supply (9) and with the finished product discharge valve (15) to the collecting container (16), as well as by a fine material feedback (11) located above the separation tube (10), which feedback discharges into the fine material cyclone (12) located above the fine material flap valve (13), as well as by a dust outlet (14), as well as by a seed particle pipe (17) discharging into the reactor chamber (4).
 20. A fluidised-bed reactor according to claim 19, characterised in that the separation tube (10) is a zigzag separation tube.
 21. The use of the fluidised-bed reactor according to claims 19 to 20 for the manufacture of highly pure, granular silicon by decomposing silicic gas. 